U.S. patent number 4,357,429 [Application Number 06/359,917] was granted by the patent office on 1982-11-02 for process for the production of alkali metal silicate-organic plastics.
Invention is credited to David H. Blount.
United States Patent |
4,357,429 |
Blount |
November 2, 1982 |
Process for the production of alkali metal silicate-organic
plastics
Abstract
Polymerable organic compounds and an epoxide compound are
emulsified with aqueous alkali metal silicate solutions then
polymerized with a catalyst such as a peroxide type catalyst
thereby producing an alkali metal silicate organic plastic which
may be used as an adhesive, as molding powder or reacted with an
organic diisocyanide to produce polyurethane silicate resins and
foams.
Inventors: |
Blount; David H. (San Diego,
CA) |
Family
ID: |
26962641 |
Appl.
No.: |
06/359,917 |
Filed: |
March 19, 1982 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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284486 |
Jul 17, 1981 |
4332712 |
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233151 |
Feb 10, 1981 |
4303768 |
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146474 |
May 5, 1980 |
4273908 |
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036350 |
May 7, 1979 |
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889932 |
Mar 27, 1978 |
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663924 |
Mar 4, 1976 |
4097424 |
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599000 |
Jul 7, 1975 |
4072637 |
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262485 |
Jun 14, 1972 |
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71628 |
Sep 11, 1970 |
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Current U.S.
Class: |
521/100; 521/122;
521/137; 521/154; 524/650; 524/788; 524/846; 528/362; 528/421 |
Current CPC
Class: |
C08G
18/302 (20130101); C08G 18/3895 (20130101); C08G
18/62 (20130101); C08G 18/6469 (20130101); C08K
3/34 (20130101); C08K 3/34 (20130101); C08L
75/04 (20130101); C08G 2140/00 (20130101) |
Current International
Class: |
C08K
3/00 (20060101); C08K 3/34 (20060101); C08G
18/00 (20060101); C08G 18/38 (20060101); C08G
18/30 (20060101); C08G 18/62 (20060101); C08G
18/64 (20060101); C08J 009/04 (); C08J
003/06 () |
Field of
Search: |
;524/650,788,846
;521/100,122,137,154 ;528/362,421 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Foelak; Morton
Parent Case Text
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a divisional of U.S. patent application Ser.
No. 284,486 filed on July 17, 1981 now U.S. Pat. No. 4,332,712,
which is a continuation-in-part of U.S. patent application Ser. No.
233,151 filed Feb. 10, 1981, now U.S. Pat. No. 4,303,768, which is
a continuation-in-part of U.S. patent application Ser. No. 146,474
filed May 5, 1980, now U.S. Pat. No. 4,273,908, which is a
continuation-in-part of my U.S. patent application Ser. No.
036,350, filed May 7, 1979, now abandoned, which is a
continuation-in-part of my U.S. patent application Ser. No.
889,932, filed Mar. 27, 1978, now abandoned which is a
continuation-in-part of my earlier U.S. patent application Ser. No.
663,924, filed Mar. 4, 1976, now U.S. Pat. No. 4,097,424, which is
a continuation-in-part of my earlier U.S. patent application Ser.
No. 599,000, filed July 7, 1975, now U.S. Pat. No. 4,072,637, which
is a continuation-in-part of my earlier U.S. patent application
Ser. No. 262,485, filed June 14, 1972, now abandoned, which is a
continuation-in-part of my earlier U.S. patent application Ser. No.
71,628, filed Sept. 11, 1970, now abandoned.
Claims
I claim:
1. The process for the production of polyurethane silicate foamed
products by the following steps:
(a) mixing and reacting an aqueous alkali metal silicate solution
in the amount of 100 parts by weight, a polymerable unsaturated
organic compound in the amount of 5 to 100 parts by weight, a mono-
or polycarboxylic acid salt forming compound in the amount of 1 to
10 parts by weight, an organic epoxide compound, selected from the
group consisting of ethylene oxide, propylene oxide,
epichlorohydrin and mixtures thereof, in the amount of 1 to 50
parts by weight, and a catalytic amount of an initiator,
thereby
(b) producing an alkali metal silicate-organic plastic, then
(c) adding and reacting 5 to 100 parts by weight of a
polyisocyanate or polyisothiocyanate, up to 10% by weight of a
polyisocyanate initiator, up to 20% by weight of an emulsifier, up
to 50% by weight of a blowing agent, and up to 20% by weight of a
foam regulator, percentages based on the weight of the reaction
mixture, thereby
(d) producing a foamed polyurethane silicate product.
2. The product produced by the process of claim 1.
3. The process of claim 1 wherein the alkali metal silicate is
selected from the group consisting of sodium silicate, potassium
silicate and mixtures thereof.
4. The process of claim 1 wherein the acid compound is selected
from the group consisting of aliphatic carboxylic acid, aliphatic
polycarboxylic acid, cycloaliphatic carboxylic acid, cycloaliphatic
polycarboxylic acid, heterocyclic polycarboxylic acid, aromatic
polycarboxylic acid, aromatic carboxylic acid, aliphatic carboxylic
acid anhydride, aromatic carboxylic acid anhydride and mixtures
thereof.
5. The process of claim 1 wherein the acid compound is adipic
acid.
6. The process of claim 1 wherein the initiator is selected from
the group consisting of organic peroxide, inorganic peroxide,
alkali metal persulfate, ammonium persulfate, a redox system.
7. The process of claim 1 wherein the polymerable unsaturated
organic compound is selected from the group consisting of vinyl
monomers, organic dienes, allyl compounds, unsaturated aliphatic
hydrocarbon compounds and mixtures thereof.
8. The process of claim 1 wherein inorganic or organic particulates
or pulverulent materials are added to the reaction mixture.
9. The process of claim 7 wherein the vinyl monomer is selected
from the group consisting of acrylate compounds, styrene, vinyl
acetate, vinyl chloride, vinylidine chloride, acrylonitrile, vinyl
toluenes, N-vinyl carbozole, vinyl pyrovidone, vinylidine cyanide,
alkyl vinyl ketones, aryl vinyl ketones, methacrylonitrile and
mixtures thereof.
10. The process of claim 7 wherein the organic diene compound is
selected from the group consisting of isoprene, chloroprene,
butadiene and mixtures thereof.
11. The process of claim 7 wherein the allyl compound is selected
from the group consisting of allyl alcohol, 3-chloropropene,
3-bromopropene, methallyl chloride and mixtures thereof.
12. The process of claim 7 wherein the unsaturated organic
aliphatic hydrocarbon is selected from the group consisting of
ethylene, propylene and mixtures thereof.
13. The process of claim 1 wherein the polyisocyanate is selected
from the group consisting of aliphatic, cycloaliphatic,
araliphatic, aromatic, heterocyclic polyisocyanates and mixtures
thereof.
14. The process of claim 1 wherein the polyisocyanate is a
phosgenation product of an aniline-formaldehyde condensation
product.
15. The process of claim 1 wherein the polyisocyanate initiator is
selected from the group consisting of tertiary amine, organic tin
compound, silaamine and mixtures thereof.
16. The process of claim 1 wherein a water-binding agent selected
from the group consisting of hydraulic cement, gypsum, burnt lime,
synthetic anhydrate and mixtures thereof, in the amount of 1 to 300
parts by weight, is added in step (c) of claim 1, thereby producing
an inorganic-organic concrete.
17. The process of claim 1 wherein 1 to 150 parts by weight of a
polyol are added in step (c) of claim 1.
18. The product produced by the process of claim 16.
19. The product produced by the process of claim 17.
20. The process of claim 1 wherein an isocyanate-terminated
polyurethane prepolymer is used as the polyisocyanate.
21. The product produced by the process of claim 20.
22. The process of claim 1 wherein up to 10% by weight of an
epoxide starting compound which contains a reactive hydrogen atom
is added in step (a) of claim 1, percentage based on the reactants
of step (a).
Description
BACKGROUND OF THE INVENTION
This invention relates to a process for the production of alkali
metal silicate organic plastics by emulsifying a polymerable
unsaturated organic compound and an organic epoxide compound with
an aqueous alkali metal solution by mixing the polymerable organic
compound and an organic epoxide compound with an aqueous solution
of alkali metal silicate then adding a salt-forming compound in the
amount up to 10%, based on the alkali metal silicate, preferably an
organic acid, while agitating thereby producing a stable emulsion.
A polymerizing catalyst such as a peroxide type catalyst is added
to the emulsion thereby producing a poly(alkali metal
silicate-polymerable organic compound epoxide compound) copolymer.
In most products an excess amount of the aqueous alkali metal
silicate may be used. The inorganic-organic plastic produced by the
process of this invention has greatly improved flame resistance
properties.
The polymerization of an alkali metal silicate with a polymerable
unsaturated organic compound was illustrated in U.S. patent
application Ser. No. 71,628, filed Sept. 11, 1970, by David H.
Blount. The alkali metal silicate is oxidized by a peroxide
initiator then polymerized with a polymerable organic compound. I
have discovered that a stable emulsion of an aqueous alkali metal
silicate and a polymerable unsaturated organic compound may be
produced by adding up to 10% by weight, percentage based on weight
of the aqueous alkali metal silicate solution, of a salt forming
compound, and mixing with the mixture of the aqueous alkali metal
silicate and polymerable compound. This stable emulsion greatly
enhances the reaction between the alkali metal silicate and
polymerable organic compound. Any suitable polymerable unsaturated
organic compound may be used in this invention that can be
polymerized in an aqueous alkali metal silicate solution in the
presence of a peroxide initiator.
The emulsions of inorganic-organic plastics may be used as an
adhesive on wood, paper, cement, plastics, ceramics, etc., as a
coating agent on wood, cement, plastics, ceramics, etc., and may be
dried or coagulated with a salt forming compound to produce a
molding powder which may be molded by heat and pressure to produce
useful objects such as knobs, handles, gears, pipes, toys, etc. The
emulsion of inorganic-organic plastics may be further reacted with
organic compounds such as polyisocyanates, isocyanates, epoxide
compounds, substituted organic compounds, water-binding agents and
many other compounds. The emulsion of inorganic-organic plastics
may be used as a cavity filler, as putty, as a caulking compound,
and in producing laminates.
It is accordingly, an object of my invention to provide novel
inorganic-organic copolymers. A further object is to provide novel
copolymers which may be used as an adhesive. A further object is to
provide novel copolymers that will react with polyisocyanates to
produce useful resinous and foam products. A further object is to
provide a process for preparing novel inorganic-organic copolymers.
Another object is to produce emulsions of inorganic-organic
copolymers which may be used to produce concrete reinforced and
reacted with inorganic-organic copolymers.
The inorganic-organic plastics may be produced by emulsifying and
reacting the following components:
Component (a) an aqueous alkali metal silicate solution;
Component (b) a polymerable unsaturated organic compound;
Component (c) a salt forming compound;
Component (d) an initiator
Component (e) an epoxide compound
Component (a)
Any suitable alkali metal silicate may be used in this invention.
Suitable alkali metal silicates include sodium, potassium and
lithium silicates. The alkali metal silicates are preferred to be
in an aqueous solution. Concentration of 10% to 70% of alkali metal
silicates in an aqueous solution or an alkali metal metasilicate
pentahydrate which has been melted to produce an aqueous solution.
The weight ratio of SiO.sub.2 :NaO may vary greatly from 3.75:1 to
1:2. Sodium silicate is the preferred alkali metal silicate.
Component (b)
Any suitable polymerable unsaturated organic compound may be used
in this invention. Suitable polymerable unsaturated organic
compounds include but not limited to vinyl monomers, organic
dienes, allyl compounds, unsaturated aliphatic hydrocarbon
compounds unsaturated fluorocarbon compounds and mixtures
thereof.
Suitable vinyl monomers include styrene, vinyl acetate acrylates,
vinyl chloride, vinylidine chloride, acrylonitrile, vinyl toluenes,
N-vinyl carbazole, vinyl pyrovidone, vinylidine cyanide, alkyl
vinyl ketones, aryl vinyl ketones, methacrylonitrile and mixtures
thereof.
Suitable organic dienes include isoprene, chloroprene, butadiene
and mixtures thereof.
Suitable allyl compounds include allyl alcohol, methallyl alcohol,
phenallyl alcohol, 3-chloropropene, 3-bromopropene, methallyl
chloride and mixtures thereof.
Suitable aliphatic hydrocarbon compound include ethylene, propylene
and mixtures thereof.
Suitable acrylate compounds include but are not limited to methyl
methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate,
butyl acrylate, pentadecyl acrylate, hexadecyl acrylate, benzyl
acrylate, cyclohexyl acrylate, phenyl ethyl acrylate, ethyl
methacrylate, methyl-chloroacrylate, 2-chloroethyl acrylate,
1,1-dihydroperfluorobutyl acrylate, lauryl acrylate,
cyclohexylcyclohexyl methacrylate, allyl methacrylate and mixtures
thereof. Acrylic acid compounds which have been reacted with an
alkali compound may be used in this invention.
Any suitable allyl halide compound having the general formula:
##STR1## wherein R is a hydrogen or a C.sub.1 to C.sub.4 alkyl
group and x represents a halogen atom may be used in this
invention. Furthermore, these compounds contain one olefinic group
of which one unsaturated carbon atom contains at least one hydrogen
atom per molecule.
Any suitable allyl-type alcohol having the general structure
formula:
may be used in this invention.
Styrene is the preferred polymerable unsaturated organic
compound.
Component (c)
Any suitable salt forming compound may be used in this invention,
such as aliphatic carboxylic acids, aliphatic acid anhydrides,
aliphatic polycarboxylic acids, cycloaliphatic carboxylic acids,
cycloaliphatic polycarboxylic acids, aromatic carboxylic acid,
aromatic polycarboxylic acids, heterocyclic polycarboxylic acids,
aliphatic carboxylic acid anhydrides, aromatic carboxylic acid
anhydrides and mixtures thereof. The organic acids may be
substituted, e.g. with halogen atoms and may be unsaturated.
Organic polycarboxylic acids are preferred. Adipic acid is the
preferred polycarboxylic acid. It is preferred to use the organic
mono-carboxylic acids with polycarboxylic acids.
Examples of suitable aliphatic acids are, but are not limited to,
acetic acid, propionic acid, formic acid, butyric acid, valeric
acid, caproic acid, undecanoic acid, palmitic acid, stearic acid,
acrylic acid, etc.
An example of suitable aliphatic acid anhydrides is acetic
anhydride, but examples are not limited to that.
Examples of suitable aromatic acids are, but are not limited to,
benzoic acid, para-aminobenzoic acid, alicylic acid, methyl
salicylates, etc.
The polycarboxylic acid may be aliphatic, cycloaliphatic, aromatic
and/or heterocyclic and may be substituted, e.g., with halogen
atoms and may be unsaturated; examples include: succinic acid,
adipic acid, sebacic acid, suberic acid, azelaic acid, phthalic
acid, phthalic acid anhydride, isophthalic acid, tetrahydrophthalic
acid anhydride, trimellitic acid, hexahydrophthalic acid anhydride,
tetrachlorophthalic acid anhydride, endomethylene
tetrahydrophthalic acid anhydride, glutaric acid anhydride, fumaric
acid, maleic acid, maleic acid anhydride, dimeric and trimeric
fatty acid such as oleic acid, optionally mixed with monomeric
fatty acids, dimethylterephthalate and bisglycol
terephthalates.
Component (d)
Any suitable organic epoxide compound may be used in this
invention. Suitable epoxide compound include ethylene oxide,
propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide,
trichlorobutylene oxide, epihalohydrins such as epichlorohydrin,
epibromohydrin and the like.
Ethylene oxide and propylene oxide and mixtures thereof are the
preferred organic epoxide compounds. Starting components which
contain reactive hydrogen atoms such as alcohols, e.g., ethylene
glycol, propylene-1,3- and -1,2-glycol, trimethylolpropane, 4,4'
dihydroxydiphenylpropane, ammonia, ethanolamine, amines, e.g.,
aniline, ammonia, ethanolamine or ethylenediamine, carbohydrates,
e.g., sucrose, dextrose or glucose, may be added to the aqueous
alkali metal silicate in an amount up to 10% by weight, percentage
based on the reactants, (a), (b), (c) and (d).
Suitable epoxide catalyst may be used with the epoxide compounds
such as e.g. organic amines, BF.sub.3 and the like.
Component (e)
Suitable initiators include but are not limited to organic and
inorganic peroxides, alkali metal persulfates, ammonium persulfate,
redox systems, aliphatic azo compounds, organic and inorganic
peroxide with organic and inorganic metal compounds. Suitable
peroxide initiators include but are not limited to hydrogen
peroxide and acyl or aryl peroxides such as p-menthane
hydroperoxide, ethyl ketone peroxide, benzoyl peroxide, acetyl
benzyl peroxide, p-chlorobenzoyl peroxide, alkoxy benzoyl peroxide,
lauroryl peroxide, dibutyryl peroxide, dicaproyl peroxide, crotonyl
peroxide, di-tert-alkyl peroxide, methyl amyl ketone peroxide,
di-tert-butyl disphosphate peroxide, peracetic acid, cyclohexyl
hypoperoxide and mixtures thereof. Suitable alkali metal
persulfates include ammonium persulfate, potassium persulfate and
sodium persulfate. Any suitable commonly known redox systems as
known in the arts may be used. Other initiator systems may be used
such as peroxides with metal compounds as activators such as ethyl
ketone peroxide with cobalt naphthenate, potassium persulfate with
ferric sulfate or cupric sulfate (0.001 to 0.002 parts by weight
per part by weight of the polymerable compound) and benzoyl
peroxide with a tertiary amine activator, such as N,N-dimethyl
aniline. The amount of the peroxide initiator needed is quite
varied and usually a catalytic amount is sufficient, but may be
added up to 0.5% based on the reaction mixture.
The polymerization may also be initiated by heat or
photosensitizers such as benzoin, biacetyl, etc., alone or with
other initiators in certain reaction.
Surface-active additives (emulsifiers and foam stabilizers) may
also be used according to the invention. Suitable emulsifiers are,
e.g., the sodium salt of ricinoleic sulphonates or of fatty acids
or salts of fatty acids with amines, e.g., oleic acid diethylamine
or stearic acid diethanolamine. The commercially available soaps
and detergents may be used. Other surface-active additives are
alkali metal or ammonium salts or sulphonic acids, e.g.,
dodecylbenzene sulphonic acid or dinaphthyl methane disulphonic
acids or fatty acids, e.g., ricinoleic acid, or of polymeric fatty
acids. Surfactants such as sodium dioctyl sulfosuccinate, potassium
dioctyl sulfosuccinate and dioctyl calcium sulfosuccinate may also
be used.
The foam stabilizers used are mainly water-soluble polyester
siloxanes. These compounds generally have a polydimethylsiloxane
group attached to a copolymer of ethylene oxide and propylene
oxide. Foam stabilizers of this kind have been described, e.g., in
U.S. Pat. No. 3,629,308. These additives are, preferably, used in
quantities of from up to 20%, based on the reaction mixture.
Further examples of surface-active additives, foam stabilizers,
cell regulators, stabilizers, flame-retarding substances,
plasticizers, dyes, fillers and fungicidal and bacteriocidal
substances which are utilized for polyurethane foams, but may also
be used in this invention, may be found in Kunststoff-Handbuch,
Volume VI; published by Vieweg and Hochtlen, Carl-Hanser-Verlag,
Munich, 1966, e.g., on pages 103 to 113. The halogenated paraffins
and inorganic salts of phosphoric acid are the preferred
fire-retardant agents.
SUMMARY OF THE INVENTION
The process for the production of alkali metal silicate organic
plastic products is simple. It is merely necessary for the
components to come together; for example, a polymerable unsaturated
compound, an organic epoxide compound, an aqueous alkali metal
silicate, up to 10% by weight of a salt forming compound,
percentage based on the weight of the alkali metal silicate, and a
suitable initiator.
The chemical reaction of this invention may take place in any
suitable physical condition. Ambient pressure is usually
satisfactory, but in certain conditions, an elevated or below
ambient pressure may be useful. In cases where the polymerable
unsaturated compound is a gas it is usually necessary to increase
the pressure until the gas is in a liquid state or decrease the
temperature until the gas is in a liquid state or use a combination
of elevated pressure and decreased temperature. The reactants may
be mixed in any suitable manner at any suitable temperature or
pressure.
The preferred method to produce an emulsion of poly(alkali metal
silicate-polymerable unsaturated organic compound-epoxide)
copolymer is to thoroughly mix an aqueous alkali metal silicate
solution in the amount of 100 parts by weight, a polymerable
unsaturated organic compound in the amount of 5 to 100 parts by
weight, an epoxide compound in the amount of 1 to 100 parts by
weight, a salt forming compound in the amount of up to 10 parts by
weight and a catalytic amount of an initiator to form a stable
emulsion then allow the mixture to react for 1 to 24 hours at any
suitable temperature and pressure.
In an alternate method the aqueous alkali metal solution, salt
forming compound initiator and optional emulsifiers, foam
regulators and fillers are thoroughly mixed then the polymerable
unsaturated organic compound and epoxide compound are added at a
suitable temperature and pressure while agitating. The mixture is
then allowed to react for 1 to 24 hours thereby producing an
emulsion of poly(alkali metal silicate-polymerable unsaturated
organic compound-epoxide) copolymer.
The copolymer produced by this invention may be used as a coating
agent, as impregnants, as adhesives for wood, paper, etc., may be
molded into useful products such as rods, sheets, blocks, etc., may
be further reacted with polyisocyanates and used as a reinforcement
for water binding compounds such as Portland cement.
Any suitable organic polyisocyanate may be used according to the
invention, including aliphatic, cycloaliphatic, araliphatic,
aromatic, heterocyclic polyisocyanates and mixtures thereof.
Suitable polyisocyanates which may be in the process of the
invention are exemplified by the organic diisocyanates which are
compounds of the general formula:
wherein R is a divalent organic radical such as an alkylene,
aralkylene or arylene. Examples of such diisocyanates are:
p,p'-diphenylmethane diisocyanate
phenylene diisocyanate
chlorophenylene diisocyanate
tolylene diisocyanate
m-xylylene diisocyanate
benzidine diisocyanate
naphthylene diisocyanate
tetramethylene diisocyanate
pentamethylene diisocyanate
hexamethylene diisocyanate
decamethylene diisocyanate
thiodipropyl diisocyanate
Other polyisocyanates, polyisothiocyanates and their derivatives
may be equally employed. Fatty diisocyanates may be equally
employed. Fatty diisocyanates of the following general formula are
also suitable: ##STR2## where x+y totals 6 to 22 and z is 0 to 2,
e.g., isocyanatostearyl isocyanate.
Other suitable polyisocyanates include
triphenylmethane-4,4',4"-triisocyanate; polyphenyl-polymethylene
polyisocyanate of the kind which may be obtained by
anilineformaldehyde condensation followed by phosgenation;
perchlorinated arylpolyisocyanates; phosgenated products of
arylaminealdehyde condensates; phosgenated products of
arylamineketone condensates; phosgenation products of condensates
of anilines alkyl-substituted on the nucleus such as tolidines,
with aldehydes or ketones such as formaldehyde, acetaldehyde,
butyraldehyde, acetone and methyl ethyl ketone and solutions of
residual isocyanates in monomeric polyisocyanates of the type
produced in the commercial production of tolylene diisocyanate,
diphenyl methane diisocyanate or hexamethylene diisocyanate.
Another group of suitable polyisocyanates are so-called modified
polyisocyanates, i.e., polyisocyanates containing carbodiimide
groups, allophanate groups, isocyanurate groups, urea groups, amide
groups, imide groups or biuret groups. Polyisocyanates suitable for
modification of this way include aliphatic, cycloaliphatic,
araliphatic, aromatic and heterocyclic polyisocyanates of the type
described, for example, by W. Siefken in Justus Liebigs, Annalen
der Chemie, 562, pages 75 to 136. Specific examples include:
ethylene diisocyanate; 1,4-tetramethylene diisocyanate;
1,6-hexamethylene diisocyanate; 1,12-dodecane diisocyanate;
cyclobutane-1,3-diisocyanate; cyclohexane-1,3- and
1,4-diisocyanates and mixtures of these isomers;
1-isocyanato-3,3,5-trimethyl cyclohexane (U.S. Pat. No. 3,401,190);
2,4- and 2,6-hexahydro tolylene diisocyanate and mixtures of these
isomers; hexahydro-1,3- and/or 1,4-phenylene diisocyanate;
perhydro-2,4'- and/or -4,4'- diphenylmethane diisocyanate; 1,3- and
1,4-phenylene diisocyanate; 2,4- and 2,6-tolylene diisocyanate and
mixtures of these isomers; diphenyl methane-2,4'- and/or
-4,4'-diisocyanate; naphthylene-1,5-diisocyanate; triphenyl
methane-4,4', 4"-triisocyanate;
polyphenyl-polymethylene-polyisocyanate of the type obtained by
condensing aniline with formaldehyde, followed by phogenation and
described in British patent Nos. 874,430 and 848,671; and
perchlorinated aryl polyisocyanates of the type described in U.S.
Pat. No. 3,277,138.
Polyisocyanates of this type are modified in well known manners
either thermally and/or catalytically by air, water, urethanes,
alcohols, amides, amines, carboxylic acids or carboxylic acid
anhydrides. Monofunctional low molecular weight alcohols
(preferably having 1 to 12 carbon atoms, such as methanol, ethanol,
n- and isopropyanol, butanol, hexanol, n-octyl alcohol and dodecyl
alcohol) may also be used as modifying agents, providing the
urethane groups formed are converted into allophanate groups by
further reactions with isocyanate present and providing the
functionality of the resulting modified polyisocyanate is not
reduced to an undesirable extent in this way. The modifying agent
should be used in small quantities of less than 10% by weight,
based on the polyisocyanate.
It is generally preferred to use commercially readily available
polyisocyanates, e.g., tolylene-2,4- and -2,6-diisocyanate and any
mixtures of these isomers which is commercially known as ("TDI"),
polyphenyl-polymethyleneisocyanates obtained by
aniline-formaldehyde condensation, followed by phosgenation which
is commercially known as ("crude TDI"), and polyisocyanates which
contain carbodiimide groups, urethane groups, allophanate groups,
isocyanurate groups, urea groups, imide groups or biuret groups
("modified polyisocyanate").
Any suitable polyhydroxyl compound may be used according to the
invention. It is preferred to use organic polyhydroxyl compounds
which contain from 2 to 8 hydroxyl groups, e.g., polyhydric
alcohols, polyesters, polyethers, polythioethers, polyacetals,
polycarbonates or polyester amides containing at least 2, generally
from 2 to 8, but preferably from 2 to 4, hydroxyl groups, of the
kind known for producing homogenous and cellular polyurethanes.
Suitable polyhydric alcohols include, but are not limited to,
ethylene glycol; propylene 1,2- and -1,3-glycol; butylene-1,4- and
-2,3-glycol; hexane-1,6-diol; octane 1,8-diol; neopentyl glycol;
cyclohexanedimethanol-(1,4-bishydroxymethylcyclohexane);
2-methyl-propane-1,3-diol; glycerol; trimethylol propane;
hexane-1,2,6-triol; butane-1,2-4-triol; trimethylol ethane;
pentaerythritol; quinitol; mannitol and sorbitol; methylglycoside;
diethylene glycol; triethylene glycol; tetraethylene glycol;
polyethylene glycols; dipropylene glycol; dibutylene glycol and
polybutylene glycols.
Suitable hyroxyl group-containing polyesters may be, for example,
reaction products of polyhydric alcohols, preferably dihydric
alcohols, with the optional addition of trihydric alcohols, and
polybasic, preferably dibasic carboxylic acids. The listed
polyhydric alcohols may be reacted with polycarboxylic acid to
produce polyester polymer containing hydroxyl groups. Instead of
the free polycarboxylic acids, the corresponding polycarboxylic
acid esters of lower alcohols or polycarboxylic acid anhydrides or
their mixtures may be used for preparing the polyesters. The
polycarboxylic acids may be aliphatic, cycloaliphatic, aromatic
and/or heterocyclic and may be substituted, e.g., with halogen
atoms, and may be unsaturated. Examples include: succinic acid,
adipic cid, suberic acid, azelaic acid, sebacic acid, phthalic
acid, isophthalic acid, trimellitic acid, phthalic acid anhydride,
tetrahydrophthalic acid anhydride, hexahydrophthalic acid
anhydride, tetrachlorophthalic acid anhydride, hexahydrophthalic
acid anhydride, tetrachlorophthalic acid anhydride, endomethylene
tetrahydrophthalic acid anhydride, glutaric acid anhydride, maleic
acid, maleic acid anhydride, fumaric acid, dimeric and trimeric
fatty acids such as oleic acid, optionally mixed with monomeric
fatty acids, dimethylterephthalate and bis-glycol
terephthalate.
Suitable polyethers with at least 2, generally from 2 to 8, and
preferably 2 to 4, hydroxyl groups may be used according to the
invention and may be prepared, e.g., by the polymerization of
epoxides such as ethylene oxide, propylene oxide, butylene oxide,
tetrahydrofuran, styrene oxide, trichlorobutylene oxide or
epichlorohydrin, each with itself, e.g., in the presence of
BF.sub.3, or by addition of these epoxides, optionally as mixtures
of successively, to starting components which contain reactive
hydrogen atoms such as alcohols or amines, e.g., water, ethylene
glycol, propylene-1,3- and -1,2-glycol, trimethylolpropane,
4,4'-dihydroxydiphenylpropane, aniline, ammonia, ethanolamine or
ethylenediamine. Sucrose polyethers such as those described, e.g.,
in German Auslegeschriften, Nos. 1,176,358 and 1,064,938, may also
be used according to this invention. Polyethers modified with vinyl
polymers such as those which may be obtained by polymerizing
styrene or acrylonitrile in the presence of polyethers, (U.S. Pat.
Nos. 3,383,351; 3,304,273; 3,523,093 and 3,110,695) and
polybutadienes which contain OH groups are also suitable.
Suitable polyacetals may be obtained from glycols, e.g., diethylene
glycol, triethylene glycol, 4,4'-dihydroxydiphenyldimethylmethane,
hexandiol, and formaldehyde. Polyacetals suitable for the invention
may also be prepared by the polymerization of cyclic acetals.
Suitable polycarbonates with hydroxyl groups may be of the kind,
e.g., those which may be prepared by reacting diols, e.g.,
propane-1,3-diol; butane-1,4-diol and/or hexane-1,6-diol or
diethylene glycol, triethylene glycol or tetraethylene glycol, with
diarylcarbonates, e.g., diphenylcarbonate or phosgene.
Suitable polythioethers are the condensation products of
thiodiglycol with itself and/or with other glycols, dicarboxylic
acids, formaldehyde, aminocarboxylic acids or amino alcohols.
Suitable polyester amides and polyamides include, e.g., the
predominantly linear condensates obtained from polyvalent saturated
and unsaturated carboxylic acids or their anhydrides and polyvalent
saturated and unsaturated amino alcohols, diamine, polyamines and
mixtures thereof.
Suitable polyhydroxyl compounds which already contain urethane,
modified or unmodified natural polyols, e.g., castor oil,
carbohydrates and starches may be used in this invention.
Additional products of alkylene oxides with phenolformaldehyde
resins or with urea-formaldehyde resins are also suitable for the
purpose of the invention.
Other compounds which contain at least 2 hydrogen atoms capable of
reacting with isocyanates may be used in this invention in place of
polyhydroxyl compound or with polyhydroxyl compounds such as
compounds containing amino groups, thiol groups or carboxyl
groups.
Examples of these compounds which are to be used according to the
invention have been described, e.g., in High Polymers, Volume XVI,
"Polyurethane, Chemistry and Technology", published by
Saunders-Frisch, Interscience and Publishers, New York, London,
Volume I, 1962, pages 32 and 42 and pages 44 to 54; and Volume II,
1964, pages 5 to 6 and 198 to 199; and in Kunststoff-Handbuch,
Volume VII, Vieweg-Hochtlen, Carl-Hanswer-Verlag, Munich, 1966, on
pages 45 to 71.
Water-binding components which may be used, according to the
invention include organic or inorganic water-binding substances
which have, first, the ability to chemically combine, preferably
irreversibly, with water and, second the ability to reinforce the
organic-inorganic end products of the invention; hold the water
chemically bound until water is released and extinguishes the fire.
The term "water-binding component" is used herein to identify a
material, preferably granular or particulate, which is sufficiently
anhydrous to be capable of absorbing water to form a solid or gel
such as mortar or hydraulic cement. This compound may be a mineral
or chemical compound which is anhydrous, such as CaO and CaSO4, but
may exist as a partial hydrate. Water-binding components used are
inorganic materials such as hydraulic cements, synthetic anhydrite
with silica or burnt lime with silica.
Suitable hydraulic cements are, in particular, Portland cement,
quick-setting cement, blast-furnace Portland cement, mild-burnt
cement, sulphate-resistant cement, brick cement, natural cement,
lime cement, gypsum cement, pozzolan cement and calcium sulphate
cement. In general, any mixture of fine ground lime, alumina and
silica that will set to a hard product by admixture of water and
which combines chemically with the other ingredients to form a
hydrate may be used. The most preferred forms of water-binding
agents to be used according to the invention are those materials
which are normally known as cement. In other words, they are a
normally powdered material with which water normally forms a paste
which hardens slowly and may be used to bind intermixed crushed
rock or gravel and sand into rockhard concrete. There are so many
different kinds of cement which can be used in the production of
the compositions of the invention and they are so well known that a
detailed description of cement will not be given here; however, one
can find such a detailed description in Encyclopedia of Chemical
Technology, Volume 4, Second Edition, Published by Kirk-Othmer,
pages 684 to 710, as well as in other well known references in this
field. In particular, pages 685 to 697 of the aforementioned Volume
4, Second Edition of Kirk-Othmer's Encyclopedia, containing a
detailed disclosure of the types of cement which may be used in the
production of the compositions of this invention, are incorporated
herein by reference.
The ratio of the essential components which lead to the production
of the polyurethane silicate foams and solid of the invention may
vary, broadly speaking, within the following ranges as follows:
(a) 100 to 200 parts by weight of an emulsion of poly (alkali
metal-polymerable unsaturated compound-epoxide compound)
copolymer;
(b) 50 to 200 parts by weight of an organic polioisocyanate or
polyisothiocyanate;
(c) up to 150 parts by weight of a polyhydroxyl compound
(polyol);
(d) up to 300 parts by weight of a water-binding compound;
(e) up to 20% by weight, based on the reaction mixture, of an
emulsifying agent, percentage based on the reaction mixture;
(f) up to 50% by weight of a blowing agent, percentage based on the
reaction mixture;
(g) up to 20% by weight of a foam stabilizer, percentage based on
the reaction mixture;
(h) up to 10% by weight of an isocyanate initiator (catalyst)
percentage based on the reaction mixture;
(i) up to 50% by weight of a filler, percentage based on the
reaction mixture.
The components may be reacted at any suitable temperature or
pressure to produce polyurethane silicate products. The components
are preferably mixed at room temperature and pressure, though any
suitable temperature in range of -20.degree. C. to 80.degree. C.
may be employed. The chemical reaction is usually exothermic, and
the temperature of the mixture is usually elevated above 30.degree.
C.
To increase the expanded volume of the foams produced by the
process according to the invention, expanding or blowing agents may
be used. Any suitable blowing agent may be used, including, for
example, inert liquids boiling at temperatures of from -25.degree.
C. to 50.degree. C. The blowing agents preferably have boiling
points of from -15.degree. C. to +40.degree. C. Particularly
suitable blowing agents are alkanes, alkenes, halogen-substituted
alkanes and alkenes or dialkyl ethers such as, for example,
saturated or unsaturated hydrocarbons with 4 to 5 carbon atoms such
as isobutylene, butane, pentane, petroleum ether, halogenated
saturated or unsaturated hydrocarbons such as chlorlmethyl,
methylene chloride, fluorotrichloromethane,
difluorodichloromethane, trifluorochloromethane, chloroethane,
trichlorofluoromethane, and C.sub.4 -hydrocarbons such as butane,
for example, which have proved to be the most suitable. Any
suitable highly volatile inorganic and/or organic substances may be
used as a blowing agent, including those listed above. Additional
suitable blowing agents are, for example, acetone, ethyl acetate,
methanol, ethanol, hexane or diethylether. Foaming can be increased
by adding compounds which decompose at temperatures above room
temperature to liberate gases such as nitrogen, for example, azo
compounds such as azoisobutyric and nitrile. Other examples of
blowing agents are included, for example, in Kunststoff Handbuch,
Volume VII, published by Vieweg and Hochtlen, Carl-Hanser-Verlag,
Munich 1966, e.g., on pages 108 and 109, 445 to 453 and 507 to 510.
Fine metal powders such as powdered calcium, magnesium, aluminum or
zinc may also be used as blowing agents when an alkali metal
silicate is added to the water by the evolving hydrogen.
The blowing agents may be used in quantities of from up to 50% by
weight and preferably in quantities of from 2 to 10% by weight,
based on the reaction mixture. The blowing agent is added
simultaneously with the components.
Inert gases, especially air, may be used as the blowing agent. For
example, one of the liquid components can be prefoamed with air and
then mixed with the other components. The components can also be
mixed by means of compressed air so that foam is directly formed,
subsequently hardening in molds.
Other substances such as the emulsifiers, activators and foam
stabilizers normally used in the production of polyurethane foams
can also be added; however, they are generally not necessary.
Silanes, polysiloxanes, polyether polysiloxanes or silyl-modified
isocyanates may be used as foam stabilizers. Examples of foam
stabilizers are disclosed in U.S. Pat. No. 3,201,372 at column 3,
line 46 to column 4, line 5 and may be added in an amount up to 20%
by weight, percentage based on the reaction mixture.
Activators (catalysts) may optionally be used in the process
according to the invention. The activators used may be known, per
se, e.g., tertiary amines such as triethylamine; tributylamine;
triethylenediamine; N-methyl-morpholine; N-ethyl-morpholine;
N-cocomorpholine; N,N,N',N'-tetramethylethylenediamine;
1,4-diaza-bicyclo-(2,2,2)-octaine;
N-methyl-N'-dimethylaminoethylpiperazine; N,N-benzylamine;
bis-(N,N-diethylaminoethyl)-adipate; N,N-diethyl benzylamine;
pentamethyl diethylenetriamine; N,N-dimethyl cyclohexalamine;
N,N,N',N'-tetramethyl-1,3-butanediamine; N,N-dimethyl-phenyl
ethylamine; 1,2-dimethyl imidazole; 2-methyl imidazole;
hexahydrotriazine derivatives; triethanolamine;
triisopropanolaimine; N-methyl-diethanolamine;
N-ethyl-diethanolamine; N,N-dimethyl-ethanolamine; and tertiary
amine reaction products with alkylene oxides such as propylene
oxide and/or ethylene oxide.
Silaamines with carbon-silicon bonds may also be used as catalysts,
e.g., those described in German Patent No. 1,229,290, for example,
2,2,4-trimethyl-2-silamorpholine or
1,3-diethylamineomethyl-tetramethyldisiloxane.
Bases which contain nitrogen such as tetraalkyl ammonium
hydroxides, alkali metal hydroxides such as sodium hydroxide,
alkali metal phenolates such as sodium phenolate or alkali metal
alcoholates such as sodium methylate may also be used as a
catalyst. Hexahydrotriazines are also suitable catalysts.
Organic metal compounds may also be used as catalysts according to
the invention, especially organic tin compounds. The organic tin
compounds used are preferably tin salts of carboxylic acids such as
tin acetate, tin octoate, tin ethyl hexoate and tin laurate and the
dialkyl tin salts of carboxylic acid such as dibutyl tin diacetate,
dibutyl tin dilaurate, dibutyl tin maleate or dioctyl tin
diacetate.
Other examples of activators which may be used according to the
invention and details of the activators (catalysts) may be found in
Kunststoff-Handbuch, Volume VII, published by Vieweg and Hochtlen,
Carl-Hanser-Verlag, Munich 1966, e.g., on pages 96 to 102.
The activator is generally used in a quantity of up to 10% by
weight, based on the reactants in the mixture, and is added
simultaneously with the other components.
Particularly high quality products are obtained by the process
according to the invention when the temperature is between
20.degree. C. and about 100.degree. C. When an alkali metal
silicate is used with water as the curing agent, the temperature is
elevated by the heat produced by the chemical reaction of
NCO-groups and alkali silicate solutions. This results in the
formation of materials which, on the one hand, are hard as stone,
but which, on the other hand, are highly elastic and, hence, highly
resistant to impact and breakage.
If the quantity of heat which is liberated during the reaction
between the components is not sufficient to obtain optimum
properties, mixing can readily be carried out at elevated
temperatures, for example, at temperature of from 30.degree. C. to
100.degree. C. In special cases, mixing can also be carried out
under pressure at temperatures above 100.degree. C. up to about
150.degree. C. in a closed container so that expansion occurs,
accompanied by foam formation, as the material issues from the
container.
Generally, production of the foams in accordance with the invention
is carried out by simultaneously mixing the components in any
suitable mixer, in a batch-type or continuous mixer, and by
allowing the resulting mixture to foam and harden in molds or on
suitable substrates, generally outside the mixture. Then after the
mixture containing water-binding agent has expanded and hardened in
the mold, water may be added to the expanded foam by any suitable
method, e.g., by spraying with water, by steaming, by soaking the
foam in water, etc. The water is absorbed by the foam and reacts
with the unreacted water-binding agent to further cure the excess
water-binding agent in the cellular solid product. The necessary
reaction temperature, amounting to between preferably about
0.degree. C. and 200.degree. C. and most preferably to between
20.degree. C. and 130.degree. C., can either be achieved by
preheating one or more reaction components before the mixing
process or by heating the mixer itself or by heating the reaction
mixture prepared after mixing. Combinations of these or other
procedures for adjusting the reaction temperature are, of course,
also suitable. In most cases, sufficient heat is generated during
the reaction itself so that after the beginning of the reaction or
foaming, the reaction temperature can rise to levels of about
100.degree. C.
For any given recipe, the properties of the resulting foams, for
example, their moist density, is governed to some extent by the
parameters of the mixing process, for example, the shape and
rotational speed of the stirrer, the shape of the mixing chamber,
etc., and also by the reaction temperature selected. The foams can
have closed or open cells although, in most cases, they are largely
made up of closed cells. Densities may be quite varied, but
densities of 0.01 and 0.8 q/cc are preferred.
In cases of high amounts of inorganic material, these foams combine
good flame resistance, insulating properties and low cost of the
starting materials.
The process according to the invention provides a number of
potential utilities as either porous or homogenous materials and,
accordingly, a few fields of application are outlined by way of the
examples which follow.
The reaction mixture, with or without a blowing agent, can be
coated for example, onto any given warm, cold or even IR- or
HF-irradiated substrates, or after passing through the mixer, can
be sprayed with compressed air or even by the airless process onto
these substrates on which it can foam and harden to give a filling
or insulating coat. This type of application may be used for
plastering the exterior or interior of a building or residence with
polyurethane silicate concrete to provide an insulating plaster
which is relatively low in cost, has good flame resistance, good
insulating properties and may be color coated or water-proof
coated.
The foaming reaction mixture can also be molded, cast or
injection-molded in cold or heated molds and allowed to harden in
these molds, whether relief or solid or hollow molds, if desired by
centrifugal casting at room temperature of up to 200.degree. C. or,
if desired, under pressure. In this respect, it is quite possible
to use strengthened elements, whether in the form of inorganic
and/or organic or metallic wires, fibers, webs, foams, woven
fabrics, skeletons, etc. This can be done, for example, by the
fiber-mat impregnating process or by processes in which reaction
mixtures and strengthening fibers are applied together to the mold;
for example, by means of a spray unit. The moldings obtainable in
this way can be used as structural elements, for example, in the
form of optionally foamed sandwich elements produced either
directly or subsequently by lamination with metal, glass, plastics,
etc., in which case the favorable flame behavior of the foams in
their moist or dry form is of particular advantage; however, they
can also be used as hollow bodies, for example, as containers for
products that may have to be kept moist or cool, active substances,
as decorative elements, as parts of furniture and as cavity
fillings. The may be used in the field of pattern and mold design,
and also in the production of molds for casting metals.
In one preferred procedure, the components containing a hydraulic
cement are mixed in a mixing chamber, then pumped to a mold such as
a concrete block mold, and the mixture expands and hardens. The
foamed block is removed from the mold.
The foams obtainable in this way can be used as insulating
materials, cavity fillings, packaging materials, building materials
with outstanding resistance to solvents and favorable flame
behavior. The foams can also be used as lightweight walls, bricks,
blocks, roof shingles or in the form of sandwich elements, for
example, with metal, plastic or wood covering layers, in houses,
vehicles and aircraft construction.
It is also possible to introduce into the foaming reaction
mixtures, providing they are still free-flowing, organic and/or
inorganic foamable or already foamed particles such as expanded
clay, expanded glass, wood, popcorn, cork, hollow beads of plastics
like vinyl chloride polymers, polyethylene, styrene polymers or
foam particles thereof or even, for example, polysulphone,
polyepoxide, polyurethane, ureaformaldehyde, phenol formaldehyde,
polyimide polymers. The reaction mixtures may be allowed to foam
through interstitial spaces in packed volumes of these particles so
as to produce insulating materials which are distinguished by
excellent flame behavior. Combination of expanded clay, glass or
slate with the reaction mixture, according to the invention, is
especially preferred.
The foaming mixture containing hydraulic cement may be sprayed in
place of stucco on houses to provide insulation. It may be used in
construction, engineering, road building, for erecting walls,
igloos, seals for filing joints, plastering, flooring, insulation,
decoration and as a coating, screen and covering material. The foam
can also be used as an adhesive, as mortar or as casting
compositions, optionally filled with inorganic or organic
fillers.
Auxillaries which may, if desired, be used in, or subsequently
introduced into, the reaction mixture, such as emulsifiers,
surfactants, dispersants, odorants or hydrophobizing substances,
enable the property spectrum of the foams in either their moist or
their dry form to be modified as required.
The cellular solid products obtained in accordance with the process
of this invention may be molded. The molds may be made of materials
including inorganic and/or organic foamed or unfoamed, materials
such as metals, for example, iron, nickel, fine steel, lacquered or
teflon-coated aluminum, procelain, glass, wood, plastics such as
PVC, polyethylene, epoxide resins, ABS, polycarbonate, etc. The
foams obtainable by the invention can be surface-treated or, where
they are in the form of substantially permeable structures such as
open-cell foams or porous materials, can even be treated by
centrifuging vacuum treatment. Similarly, the dry molded products
can also be after-treated by rinsing or impregnating with aqueous
or non-aqueous acid, neutral or basic liquids or gases such as
inorganic or organic acids, ammonia, amines, organic or inorganic
salt solutions, lacquer solutions, solutions of polymerizable or
already polymerized monomers, dye solutions, galvanizing baths,
solutions of catalysts or catalyst preliminary stages, odorants and
the like.
The cellular solid products produced by the invention can be
subsequently lacquered, metallized, coated, laminated, galvanized,
subjected to vapor deposition, bonded or flocked in their moist or
dry form or in impregnated form. The cellular solid products can be
further processed for example, by sawing, milling, drilling,
planing, polishing and other machining techniques. The cellular
solid products may be modified in their properties by thermal
after-treatment, oxidation processes, hot-pressing, sintering
processes or surface melting or other consolidation processes.
The new cellular solid products are particularly suitable for use
as structural materials because they show tensile and compressive
strength, are tough, rigid and, at the same time, elastic. They
show high permanent dimensional stability when hot, are
substantially non-inflammable, and have excellent heat-insulating
and sound-insulating properties. High quality, lightweight
structural panels and complicated moldings may be made, optionally
under pressure, from the products of this invention. It is also
possible, by adopting a suitable procedure, to produce molding with
an impervious outer skin. When a technique of foaming in the mold
under pressure is employed, molded parts with dense marginal zones
and completely non-porous, smooth surfaces are obtained.
Fillers in the form of particulate or powdered materials can be
additionally incorporated into the mixtures of organic
polyisocyanates and poly(alkali metal silicate-polymerable
unsaturated organic compounds) copolymers for a number of
applications.
Suitable fillers include solid inorganic or organic substances, for
example, in the form of powders, granulates, wire fibers,
dumb-bells, crystallites, spirals, rods, beads, hollow beads, foam
particles, webs, pieces of woven fabric, knot fabrics, ribbons,
pieces of film, etc., for example, of dolomite, sand, crushed
rocks, chalk, alumina, asbestos, iron oxide, aluminum oxide and
oxide hydrates, zeolites, basalt wool or powder, glass fibers,
C-fibers, graphite, carbon black, Al-, Fe-, Cu-, Ag-powder,
molybdenum sulphite, steel wool, bronze or copper cloth, silicon
powder, expanded clay particles, hollow glass beads, glass powder,
lava and pumice particles, wood chips, sawdust, cork, cotton,
straw, jute, sisal, hemp, flax, rayon, popcorn, coke, particles of
filled or unfilled, foamed or unfoamed, stretched or unstretched
organic polymers, including plastics and rubber waste. Of the
numbers of suitable organic polymers, the following, which can be
present in the form of foam particles, granulate, powder, hollow
beads, beads, foamable or unfoamed particles, fibers, ribbons,
woven fabrics, webs, etc., are mentioned purely by way of example:
polystyrene, polyethylene, polypropylene, polyacrylonitrile,
polybutadiene, polyisoprene, polytetrafluoroethylene, aliphatic and
aromatic polyesters, melamine-urea or phenol resins, polyacetal
resins, polyepoxides, polyhydantoins, polyureas, polyethers,
polyurethanes, polyimides, polyamides, polysulphones,
polycarbonates, and, of course, any copolymer as well. Inorganic
fillers are preferred.
Generally, the composite materials according to the invention can
be filled with considerable quantities of fillers without losing
their valuable property spectrum. The amount of fillers can exceed
the amount of the components. In special cases, the
inorganic-organic components of the present invention act as a
binder for such fillers.
A high-boiling aromatic ester plasterizer such as a benzoate or
phthalate ester, or polyester benzoate, e.g., dipropylene glycol
benzoate, dodecyl phthalate or propylene glycol phthalate, may be
added in certain applications to the polyisocyanate or poly(alkali
metal silicate-polymerable organic compound-epoxide) copolymer in
an amount up to 50% by weight, based on the polyisocyanate or
poly(alkali metal silicate-polymerable organic compound-epoxide)
copolymer depending on which the plasterizer is added to.
A resin extender may be added, in certain applications, (in an
amount up to 50% by weight) to the polyisocyanate such as coal tar,
e.g., Allied Chemical 439 oil, a high-boiling coal tar distillate
having a Brookfield viscosity at 160.degree. F. of 14 to 33 c.p.,
mineral oil and poly-alphamethyl styrene, e.g., Dow Resin 276-V2.
Other types of polymer may also be added to the polyisocyanate.
DESCRIPTION OF PREFERRED EMBODIMENTS
My invention will be illustrated in greater detail by the specific
examples which follow, it being understood that these preferred
embodiments are illustrative of, but not limited to, procedures
which may be used in the production of alkali metal silicate
organic plastic products. Parts and percentages are by weight
unless otherwise indicated.
EXAMPLE 1
Sodium metasilicate pentahydrate is melted to produce an aqueous
solution of sodium metasilicate, then mixed with an equal amount by
weight of an equal mixture of propylene oxide and styrene; then 5%
by weight of adipic acid, percentage based on weight of sodium
metasilicate are added and thoroughly mixed thereby producing a
stable emulsion of styrene and propylene oxide in the aqueous
solution of sodium metasilicate. About 0.1% by weight of benzoyl
peroxide percentage based on weight of reactant and about 0.05%
cobalt naphthenate is thoroughly mixed in the emulsion. The mixture
is polymerized in 1 to 24 hours to produce an emulsion of
poly(sodium silicate-styrene-propylene oxide) copolymer.
The emulsion may be diluted with water or dilute sodium hydroxide
solution to obtain the desired viscosity, the desired color pigment
added, then painted on new or cured concrete floor, stairs or
blocks for a coating agent to improve water resistance and for
decoration.
EXAMPLE 2
About 30 parts by weight of an aqueous sodium silicate solution
containing 14.7% Na.sub.2 O and 29.4% SiO.sub.2 by weight, 20 parts
by weight of styrene, 5 parts by weight of propylene oxide, 0.5
parts by weight of the sodium salt of ricinoleic sulphonates and 1
part by weight of benzoic acid are thoroughly mixed and emulsified;
then 0.1 part by weight of potassium persulfate, 0.01 part by
weight of ferric sulfate and 0.1 part by weight of benzoyl peroxide
is added to the emulsion and thoroughly mixed at ambient
temperature (24.degree. C.) and pressure. The mixture is
polymerized in 1 to 24 hours thereby producing a poly(sodium
silicate-styrene-propylene oxide) copolymer emulsion.
EXAMPLE 3
Poly(sodium silicate-vinyl acetate-propylene oxide) copolymer
emulsion is produced by mixing and reacting the following
components for 1 to 24 hours:
(1) 30 parts by weight of an aqueous sodium silicate solution
containing 19.7% Na.sub.2 O and 31.5% SiO.sub.2 by weight;
(2) 15 parts by weight of vinyl acetate;
(3) 10 parts by weight of propylene oxide;
(4) 0.2 parts by weight of p-menthane hyperperoxide, 0.02 parts by
weight of cupric sulfate and 0.8 parts by weight of testdodecyl
mercaptan.
The emulsion is diluted with a dilute aqueous sodium hydroxide
solution until the desired viscosity is obtained then used as a
binder by mixing with cellulose fibers. The wet cellulose fibers
are placed on a small sheet-making machine thereby producing
handsheets which are then fired at about 160.degree. F.
EXAMPLE 4
About 30 parts by weight of an aqueous sodium silicate solution
containing 18% Na.sub.2 O and 36% SiO.sub.2 by weight, 10 parts by
weight of acrylonitrile, 10 parts by weight of propylene oxide, 1
part by weight of glyceral, 1 part by weight of para aminobenzoic
acid, 0.01 part by weight of ferric sulfate are thoroughly mixed
thereby producing a stable emulsion. The mixture is reacted at
ambient temperature and pressure for 1 to 24 hours thereby
producing a poly(sodium silicate-acrylonitrile-propylene oxide)
copolymer emulsion.
EXAMPLE 5
About 50 parts by weight of an aqueous sodium silicate solution
containing about 10% Na.sub.2 O and 25% SiO.sub.2 by weight, 25
parts by weight of methyl methacrylate, 10 parts by weight of
propylene oxide, 2 parts by weight of phthalic anhydride, 5 parts
by weight of sodium hydroxide and 0.5 parts by weight of benzoyl
peroxide are thoroughly mixed thereby producing an emulsion. The
mixture is reacted at ambient temperature and pressure for 1 to 24
hours thereby producing a poly(sodium silicate-methyl
methacrylate-propylene oxide) copolymer emulsion.
Other acrylate compounds may be used in place of methyl
methacrylate such as methylacrylate, ethyl acrylate,
propylacrylate, butyl acrylate, pendecyl acrylate, hyxodecyl
acrylate, benzyl acrylate, cyclohexyl acrylate, phenyl ethyl
acrylate, ethyl methacrylate, methyl.alpha.-chloroacrylate,
2-chloroethyl acrylate, 1,1-dihydroperfluorobutyl acrylate, lauryl
acrylate, cyclohexylcyclohexyl methacrylate, methacrylate, allyl
methacrylate, ethylene methacrylate, n-butyl methacrylate and the
like and mixtures thereof.
The emulsion may be used as an adhesive by applying to two pieces
of boards then placing them together to dry.
EXAMPLE 6
About 50 parts by weight of an aqueous sodium silicate solution
containing about 10% Na.sub.2 O and 20% SiO.sub.2 by weight, 40
parts by weight of isoprene, 5 parts by weight of propylene oxide,
2 parts by weight of adipic acid, 0.5 parts by weight of potassium
persulfate and 0.01 part by weight of ferric sulfate are thoroughly
mixed thereby producing a stable emulsion. The mixture is reacted
at a temperature and pressure to keep the temperature just below
the boiling temperature of isoprene for 1 to 24 hours thereby
producing a poly (sodium silicate-isoprene propylene oxide)
copolymer emulsion.
Other organic dienes may be used in place of isoprene such as
chloroprene, butadiene and mixtures thereof, at a temperature and
pressure where the organic diene is in a liquid state.
The emulsion may be used in construction as a caulking compound
around windows and doors.
EXAMPLE 7
About 50 parts by weight of an aqueous sodium silicate solution
containing 12.45% Na.sub.2 O and 32.1% SiO.sub.2 by weight, 20
parts by weight of vinyl pyrrolidone, 15 parts by weight of
propylene oxide, 0.05 parts by weight of hydrogen peroxide (aqueous
solution containing about 30% H.sub.2 O.sub.2), 0.01 part by weight
of cupric sulfate and 1 part by weight of acetic acid are
thoroughly mixed thereby producing an emulsion. The mixture is
polymerized in 1 to 24 hours thereby producing a poly(sodium
silicate-vinyl pyrrolidone-propylene oxide) copolymer emulsion.
EXAMPLE 8
About 50 parts by weight of an aqueous potassium silicate solution
containing about 10% K.sub.2 O and 15% SiO.sub.2 by weight, 10
parts by weight of allyl chloride, 20 parts by weight of propylene
oxide, 2 parts by weight of adipic acid, 1 part by weight of
calcium salt of stearic acid, 0.05 parts by weight of potassium
persulfate and 2 parts by weight of adipic acid are thoroughly
mixed at ambient temperature and pressure thereby producing a
stable emulsion. The mixture is polymerized in 1 to 24 hours
thereby producing a poly(potassium silicate-allyl
chloride-propylene oxide) copolymer emulsion.
The emulsion may be used as an adhesive for glueing paper together
or may be reacted with organic diisocyanates to produce foam for
insulation.
Other allyl halide compounds may be used in place of allyl chloride
such as allyl bromide, methallyl chloride, methallyl bromide, and
the like.
EXAMPLE 9
About 50 parts by weight of an aqueous sodium silicate solution
containing about 10% Na.sub.2 O and 15% SiO.sub.2 by weight, 0.05
parts by weight of potassium persulfate, 0.1 part by weight of
calcium octanoate, 0.2 parts by weight of lithium stearate and 2
parts by weight of adipic acid is added to a 2 quart capacity
reactor equipped with a stirrer and a pressure gauge. The closed
reaction was swept free of air with a nitrogen purge. About 30
parts by weight of vinyl chloride monomer and 10 parts by weight of
ethylene oxide was slowly added to the reactor while agitating at
about 50.degree. C. and at a pressure between 7 to 8 kg per
cm.sup.2 for about 12 hours thereby producing a poly(sodium
silicate-vinyl chloride-ethylene oxide) copolymer emulsion.
EXAMPLE 10
About 50 parts by weight of an aqueous sodium silicate solution
containing about 15% Na.sub.2 O and 25% SiO.sub.2 by weight, 10
parts by weight of propylene oxide, 2 parts by weight of adipic
acid, 0.2 parts by weight of sodium stearate and 0.1 part by weight
of benzoyl peroxide are mixed then added to an autoclave and a
temperature of about 50.degree. C. is maintained at a pressure
between 7.0 and 7.1 kg per cm.sup.2. Vinyl chloride monomer is
slowly added while agitating over a period of 7 to 10 hours until
the emulsion contains about 30% vinyl chloride polymerized with the
sodium silicate and propylene oxide thereby producing an emulsion
of poly(sodium silicate-vinyl chloride-propylene oxide)
copolymer.
The emulsion may be applied to paper and used as an adhesive or
used as a coating agent for wood.
EXAMPLE 11
About 50 parts by weight of an aqueous sodium silicate solution
containing about 14.7% Na.sub.2 O and 29.4% SiO.sub.2 by weight, 2
parts by weight of para-aminobenzoic acid, 0.5 parts by weight of
sodium lauryl sulphate, 0.05 parts by weight acetyl peroxide, 0.05
parts by weight of benzoyl peroxide, 10 parts by weight of
propylene oxide, 2 parts by weight of surcose, and 30 parts by
weight of vinylidene chloride are mixed thoroughly thereby forming
a stable emulsion. The mixture is polymerized in 1 to 24 hours
thereby producing a poly(sodium silicate-vinylidene
chloride-propylene oxide) copolymer emulsion.
Other vinyl monomers may be used in place of vinylidene chloride
such as divinyl benzenes, n-vinyl carbazole, arylvinyl ketones,
alkyl vinyl ketones, vinyl pyridines, vinyl pyrrolidone, vinyl
acetate, acrylonitrile, methacrylonitrile, styrene, methacrylate
and mixtures thereof.
Other organic epoxide compounds may be used in place of propylene
oxide such as, styrene oxide, epichlorohydrin, butylene oxide,
tetrahydrofuran, trichlorobutylene oxide and the like.
EXAMPLE 12
About 50 parts by weight of an aqueous sodium silicate solution
containing about 13% Na.sub.2 O and 25% SiO.sub.2 by weight, 2
parts by weight of phthalic anhydride, 10 parts by weight of
acrylonitrile, 5 parts by weight methallyl chloride, 10 parts by
weight of propylene oxide, 0.5 parts by weight of potassium fatty
acid soap, 0.05 parts by weight of potassium persulfate, 0.05 parts
by weight of benzoyl peroxide and 0.01 parts by weight of cupric
sulfate are thoroughly mixed thereby forming a stable emulsion. The
mixture is occasionally agitated at ambient temperature and
pressure and is polymerized in 1 to 24 hours thereby producing a
poly(sodium silicate-methallyl chloride-acrylonitrile-propylene
oxide) copolymer emulsion.
Other vinyl monomers may be used in place of acrylonitrile such as
methyl methacrylate, styrene divinyl benzenes, methacrylonitrite,
n-vinyl carbozole, aryl vinyl ketones, alkyl vinyl ketones, vinyl
pyridines, vinyl pyrrolidone, vinyl acetate, ethylacrylate and the
like.
Other allyl compound may be used in place of methallyl chloride
such as allyl chloride, allyl alcohol, allyl bromide and the
like.
EXAMPLE 13
About 50 parts by weight of an aqueous sodium silicate solution
containing 10% by weight Na.sub.2 O, and 20% by weight SiO.sub.2, 2
parts by weight of adipic acid, 10 parts by weight of propylene
oxide, 1 part by weight sodium salt of fatty acids and a redox
system containing 0.006 parts by weight of potassium persulfate and
0.1 parts by weight of dodecyl mercaptan are mixed and cooled to
about -5.degree. C. in a closed system; then 20 parts by weight of
butadiene in a liquid state at about -5.degree. C. added to the
mixture and thoroughly mixed thereby producing a stable emulsion.
The mixture is polymerized in 1 to 24 hours to produce an emulsion
of poly(sodium silicate-butadiene-propylene oxide) copolymer.
The emulsion may be applied to two wood (board) surfaces then the
wood is placed together and the emulsion acts as a strong adhesive
when dried in 24 hours.
EXAMPLE 14
About 50 parts by weight of an aqueous sodium silicate solution
containing about 10% Na.sub.2 O and 15% SiO.sub.2, 1 part by weight
of adipic acid, 20 parts by weight of butadiene, 5 parts by weight
of propylene oxide, 0.5 parts by weight of sodium salt of fatty
acids, 0.05 to 0.1 parts by weight of ferric sulfate, 0.1 parts by
weight of hydrogen peroxide, 0.01 parts by weight of benzoxyl
peroxide and 0.1 parts by weight of lauryl mercaptan are mixed in a
closed system at ambient to 50.degree. C. while agitating at about
0.40 to 6 psiq for 30 to 120 minutes; then the mixture is heated to
70.degree. to 100.degree. C. at ambient pressure for 10 to 30
minutes. The reaction is complete within 24 hours thereby producing
an emulsion of poly(sodium silicate-butadiene-propylene oxide)
copolymer.
The emulsion may be used as a caulking compound in
construction.
EXAMPLE 15
About 60 parts by weight of an aqueous sodium silicate solution
containing about 15% Na.sub.2 O and 20% SiO.sub.2 by weight, 20
parts by weight of butadiene, 10 parts by weight of styrene, 10
parts by weight of acrylonitrile, 5 parts by weight of propylene
oxide, 2 parts by weight of adipic acid, 3 parts by weight of
potassium salt or fatty acids, 1 part by weight of trisodium
phosphate dodecahydrate, 0.2 parts by weight of diethylenetriamine,
0.2 parts by weight of diethylenetriamine, 0.2 parts by weight of
p-menthane hydroperoxide, 0.005 parts by weight of ferrous sulfate
and 0.3 parts by weight of tert-dodecyl mercaptan are added to a
closed system and are mixed thoroughly under 45 to 60 psiq and at
5.degree. C. to 50.degree. C. in a closed system, thereby producing
a stable emulsion. The reaction is complete within 24 hours thereby
producing an emulsion of poly(sodium
silicate-butadiene-styrene-acrylonitrile-propylene oxide)
copolymer.
The emulsion may be dried, then powdered, then molded by heat and
pressure into useful products such as sheets, tubes, knobs,
etc.
EXAMPLE 16
About 50 parts by weight of an aqueous sodium silicate solution
containing about 10% by weight of Na.sub.2 O and 20% by weight of
SiO.sub.2, 10 parts by weight of isoprene, 10 parts by weight of
allyl chloride, 10 parts by weight of vinylidine chloride, 5 parts
by weight of propylene oxide, 2 parts by weight of sodium salt of
fatty acids, 2 parts by weight of sodium salt of fatty acids, 2
parts by weight of adipic acid, 0.5 parts by weight of benzoyl
peroxide and 0.01 N,N-dimethyl aniline are thoroughly mixed thereby
producing a stable emulsion at ambient temperature and pressure.
The reaction is complete in 1 to 24 hours thereby producing an
emulsion of poly(sodium silicate-allyl chloride-isoprene-vinylidene
chloride propylene oxide) copolymer.
The emulsion may be painted in wood and used as an adhesive or
coating agent.
EXAMPLE 17
About 60 parts by weight of an aqueous sodium silicate solution
containing about 15% by weight of Na.sub.2 O and 25% by weight of
SiO.sub.2, 5 parts by weight of chloroprene, 5 parts by weight of
allyl alcohol, 5 parts by weight of vinylbenzyl alcohol, 5 parts by
weight of styrenne, 5 parts by weight of propylene oxide, 1 part by
weight of citric acid, 1 part by weight of aminobenzoic acid, 2
parts by weight of sodium salt of fatty acids, 0.1 parts by weight
of hydrogen peroxide, 0.05 parts by weight of benzoyl peroxide and
0.1 part by weight of azo-bisisobutyronitrile, are thoroughly mixed
in a closed system thereby producing a stable emulsion. The
emulsion is heated to 80.degree. to 100.degree. C. under autogenous
pressure for 1 to 24 hours thereby producing an emulsion of
poly(sodium silicate-unsaturated organic compound-propylene oxide)
copolymer.
The emulsion may be used as caulking material in construction to
seal around doors and window.
EXAMPLE 18
About equal parts by weight of a polyisocyanate listed below and an
emulsion of poly(sodium silicate-unsaturated compound-epoxide
compound) copolymer as produced in the Examples listed below are
thoroughly mixed at ambient temperature and pressure and reacts
within 15 seconds to 5 minutes to produce a polyurethane silicate
resinous product.
______________________________________ EXAM- Emulsion Produced PLE
in Example No. Polyisocyanate
______________________________________ a Example 1
polyphenyl-polymethylene- isocyanates with an isocyanate content of
about 5% by weight. b Example 2 tolylene diisocyanate c Example 3
p,p' diphenylmethane diisocyanate d Example 4
polyphenyl-polymethylene-iso- cyanates with an isocyanate con- tent
of about 23% by weight. e Example 5 polyphenyl-polymethylene-
polyisocyanate with an iso- cyanate content of about 2.5% by weight
f Example 6 4,4'-phenylmethylene diisocya- nate. g Example 7
polyphenyl-polymethylene- isocyanates with an isocyan- ate content
of about 23% by weight. h Example 8 polyphenyl-polymethylene-
isocyanates with an iso- cyanate content of about 15% by weight. i
Example 9 polyphenyl-polymethylene- isocyanate with an isocya- nate
content of about 7% by weight. j Example 10 Tolylene diisocyanate k
Example 11 4,4'-phenylmethylene diiso- cyanate. l Example 12
isocyanate-terminated poly- ethylene (NCO content 19% by weight). m
Example 13 polyphenyl-polymethylene- isocyanates with an isocya-
nate content of about 18% by weight. n Example 14 tolylene
diisocyanate o Example 15 4,4'-phenylmethylene diisocyanate. p
Example 16 Sulphonated polyphenyl- polymethylene-polyisocyanate. q
Example 17 Residue of tolylene diisocyanate distilla- tion (18% by
weight of NCO) r Example 18 25% solution of toly- lene diisocyanate
re- sidue polyphenyl-poly- methylene-polyisocyanate (NCO content
30%) ______________________________________
EXAMPLE 19
About equal parts by weight of an isocyanate-terminated
polyurethane prepolymer listed below and an emulsion of poly(sodium
silicate-unsaturated compound-epoxide compound) copolymer as
produced in the examples listed below are thoroughly mixed at
ambient temperature and pressure. The mixture reacts within 15
seconds to 5 minutes to produce a polyurethane silicate resinous
product.
______________________________________ EX- AM- Emulsion Produced
Isocyanate-terminated polyurethane PLE In Example No. Prepolymer
______________________________________ a Example 1
isocyanate-terminated polyethylene ether (NCO content 19% by
weight) b Example 2 isocyanate-terminated polypropylene ether (NCO
content 22% by weight) c Example 3 isocyanate-terminated polyester
(NCO content 11% by weight) d Example 4 isocyanate-terminated
polybutadiene (NCO content 15% by weight) e Example 5
isocyanate-terminated polyisocyanate silicate (NCO content 12% by
weight) f Example 6 isocyanate-terminated polysulfide (NCO content
15% by weight). ______________________________________
EXAMPLE 20
About 50 parts by weight of a polyisocyanate listed below and 60
parts by weight of an emulsion of poly(sodium silicate-unsaturated
organic compound-epoxide compound) copolymer as produced in the
example listed below, 5 parts by weight of
trichlorotrifluoroethane, 0.5 parts by weight of
triethylenediamine, 0.001 parts by weight of tin octoate are
thoroughly mixed. The mixture begins to expand in 15 to 120 seconds
to 3 minutes thereby producing a foamed polyurethane resinous
product.
______________________________________ EX- AM- Emulsion Produced
PLE in Example Number Polyisocyanate
______________________________________ a Example 1
polypheny-polymethylene- isocyanates with an NCO content of about
12%. b Example 2 tolylene diisocyanate c Example 3
4,4'-phenylmethylene diisocyanate d Example 4 4,4'-phenylmethylene
diisocyanate e Example 5 sulphonated polyphenyl-
polymethylene-polyisocyanate f Example 6 residue of tolylene
diisocyanate distil- lation (approximately 18% by weight of NCO) g
Example 7 Equal parts by weight if tolylene diisocyanate and
polyphenyl-poly- methylene-isocyanates with an isocyanate content
of 2.5%. ______________________________________
The foamed polyurethane silicate may be used to produce
construction panels, lightweight building blocks, foamed on walls
for insulation, door cores and as decorative items.
EXAMPLE 21
About 50 parts by weight of polyphenyl-polymethylene-isocyanates
with an NCO content of about 23% by weight, 40 parts by weight of
an emulsion of poly(alkali metal silicate-unsaturated
compound-epoxide compound) copolymer as produced in the examples
listed below, 20 parts by weight of a polyol listed below, 5 parts
by weight of trichlorotrifluoroethane, 2 parts by weight of
methylene chloride, 1 part by weight of a silicone surfactant
(L-5740 produced by Union Carbide), 0.05 parts by weight of
triethylamine and 0.005 parts by weight of tin laurate are
thoroughly mixed. The mixture begins to expand in 15 seconds to 3
minutes thereby producing a foamed polyurethane silicate resinous
product.
______________________________________ EX- EMULSION AM- PRODUCED
PLE IN EXAMPLE POLYOL ______________________________________ a
Example 1 Ethylene glycol (mol. wt. 600) b Example 2 Propylene
glycol (mol. wt. 600) c Example 3 Propylene glycol (mol. wt. 1200)
d Example 4 Sucrose amine polyol with a hydroxyl No. 530 and
viscosity of 11,000 (cps) e Example 5 Polyethylene triol with a
hydroxyl No. 56, 2000 mol wt. f Example 6 Phenolic based polyol,
hydroxyl No. 515-545, viscosity of 20,000-25,000. g Example 7
powdered wood h Example 8 powdered bark i Example 9 polybutadiene
polymer containing OH groups (Poly bd R-45M produced by ARCO) j
Example 10 Polyester resin terminated in OH groups k Example 11
polyethylene diol and mol wt. 1000.
______________________________________
EXAMPLE 22
Example 21 is modified by adding about 200 parts by weight of a
water-binding agent, Portland Cement to the mixture thereby
producing a foamed polyurethane silicate concrete product.
Other water-binding agents may be used in place of Portland Cement
such as other hydraulic cements, gypsum, burnt lime, synthetic
anhydrites and mixtures thereof.
EXAMPLE 23
Example 20 is modified wherein an amount of Portland cement equal
to the weight of the isocyanate-terminated polyurethane prepolymer
is added to the mixture with the other components thereby producing
a polyurethane silicate resinous concrete product.
Other water-binding agents may be used in place of Portland Cement
such as other hydraulic cements, gypsum, burnt lime, synthetic
anhydrites and mixtures thereof.
The polyurethane silicate resinous concrete may be used to produce
building panels.
EXAMPLE 24
Example 14 is modified wherein 50 parts by weight of Portland
Cement is added to the stable emulsion and thoroughly mixed then
poured into a closed mold and within 24 hours a poly(sodium
silicate butadiene-propylene oxide) copolymer reinforced concrete
is produced.
EXAMPLE 25
About 50 parts by weight of the emulsion of poly(sodium
silicate-allyl chloride-isoprene-vinylidene-propylene oxide)
copolymer as produced in Example 17, 50 parts by weight of water,
150 parts by weight of Portland cement and 150 parts by weight of
plaster's sand are thoroughly mixed then poured into a building
block mold and is cured thereby producing an inorganic-organic
plaster reinforced building block.
EXAMPLE 26
About 20 parts by weight of the emulsion of poly(sodium
silicate-styrene-propylene oxide) copolymer as produced in Example
2, 30 parts by weight of water and 100 parts by weight of gypsum
are thoroughly mixed then poured into a mold of an art object
thereby producing an inorganic-organic plastic reinforced art
object.
EXAMPLE 27
About 50 parts by weight of an aqueous sodium silicate containing
about 10% by weight of Na.sub.2 O and 15% by weight of SiO.sub.2, 2
parts by weight of adipic acid, 10 parts by weight of methyl
methacrylate, 5 parts by weight of propylene oxide, 1 part by
weight of sodium salt of fatty acids, 3 parts by weight of sodium
hydroxide, 0.1 part by weight of potassium persulfate, 0.01 part by
weight of benzoyl peroxide and 0.005 parts by weight of ferric
sulfate are thoroughly mixed to produce a stable emulsion then
poured into a closed system then 15 parts by weight of ethylene are
slowly added while agitated for 30 to 120 minutes at ambient to 60
psiq and ambient temperature. The mixture is then heated to
80.degree. to 100.degree. C. while agitating. The reaction is
complete within 24 hours thereby producing an emulsion of
poly(sodium silicate-ethylene-methyl methacrylate-propylene oxide)
copolymer.
The emulsion may be painted on wood for a coating agent.
EXAMPLE 28
About 50 parts by weight of an aqueous sodium silicate solution
containing about 10% Na.sub.2 O and 15% SiO.sub.2, 5 parts by
weight of propylene oxide, 10 parts by weight of styrene, 0.5 parts
by weight of potassium salt of fatty acids, 0.1 part by weight of
potassium persulfate, 0.01 parts by weight of ferric sulfate, 2
parts by weight of adipic acid, and 0.01 parts by weight of benzoyl
peroxide are thoroughly mixed thereby producing a stable emulsion.
About 10 parts by weight of propylene are slowly added while
agitating at ambient pressure to 60 psiq in a closed system at
ambient temperature for 30 to 120 minutes. The mixture is then
heated to 80.degree. to 100.degree. C. while agitating for 10 to 30
minutes. The reaction is complete within 1 to 24 hours thereby
producing an emulsion of poly(sodium
silicate-propylene-styrene-propylene oxide) copolymer.
The emulsion may be reacted with a polyisocyanate to produce a
foamed product which may be used for sound and thermal
insulation.
Although specific conditions and ingredients have been described in
conjunction with the above examples of preferred embodiments these
may be varied, and other reagents and additives may be used where
suitable, as described above, with similar results.
Other modifications and applications of this invention will occur
to those skilled in the art upon reading this disclosure. These are
intended to be included within the scope of this invention, as
defined in the appended claims.
* * * * *